Manufacture of phosphoric acidgroup iv metal oxide containing catalyst



Patented Oct. 20, 19E? TENT A OFFICE MANUFACTURE OF PHOSPHORIC ACID- GROUP IV METAL OXIDE CONTAINING CATALYST Mitchell s. Bielawski, Berwyn, and Julian M. Mavity, Hinsdale, 111., assignors to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application April 12, 1949, Serial. No. 87,133

9 Claims. (01. 252-435) production of a particular type of solid catalyst which has special properties both in regard to its activity in accelerating and directingolefin polymerization reactions, in its stability in service, and in its relatively low corrosive properties when employed in ordinary commercial apparatus comprising various types of steel.

An object of this invention is a method of producing a hydrocarbon conversion catalyst which has a high resistance to crushing during use. i

Another object of this invention is a highly active catalyst suitable for use in the polymerization of olefinic hydrocarbons and in other hydrocarbon conversion reactions involving olefins.

One specific embodiment of this invention re-' lates to a process for manufacturing a solid catalyst which comprises mixing a phosphoric acid, a siliceous adsorbent, and a member of the group consisting of an oxide, a hydroxide, and a salt of a metal selected from the members of the left hand fcolumn of group IV of the periodic table, drying and calcining the resultant mixture.

relates to a process for manufacturing a solid catalyst which comprisesmixing ;a phosphoric acid, a siliceous adsorbent, and thorium oxide, drying and calcining the resultant mixture. An additional embodiment of this invention relates to a process for manufacturing a solid catalyst which comprises mixing a polyphosphoric acid, diatomaceous earth, and a member of the group consisting of an oxide, a hydroxide, and a salt of a metal selected from the members of the left hand column of group IVof the peri odic'table to form a composite, drying'and calcining said composite. The essential and active ingredient of the solid catalysts which are manufactured by the present process for use in organic reactions is an acid 2 of phosphorus, preferably one in which the phosphorus has a valence of 5. The acid may constitute to about or more of the catalyst mixture ultimately produced, and in most cases is over 50% by weight thereof. Of the various acids of phosphorus, ortho-phosphoric acid (H3PO4) and pyro-phosphoric acid '(H4P2O7) find general application in the primary mixtures, due mainly to their cheapness and to the readi-. ness with which they may be'procured, although the invention is not restricted to their use but may employ any of the other acids of phosphorus insofar as they are adaptable. It is not intended to infer, however, that the different acids of phosphorus, which may be employed will produce catalysts which have identical efiects upon any given organic reactions as each of the cat' alysts produced from difierent acids and by slightly varied procedure will exert its own characteristic action.

In using ortho-phosphoric acid as a primary ingredient, different concentrations of the aqueous solution may be employed from approximately 75 to or acid containing some free phosphorus pentoxide may even be used. By this is meant thatthe ortho acid may contain a definite percentage of the pyro acid corresponding to the primary phase of dehydration of the ortho-phosphoric acid. Within these concentration ranges, the acids will be liquids of varying viscosities, and readily mixed with adsorbent materials. In practice it has been found that pyro-phosphoric acid corresponding to the formula H4P2O7 can be incorporated with siliceous adsorbents at temperatures somewhat above its melting point (142 F.) and that the period of heating which is given to the pyro acid-adsorbent mixtures maybe different from that used when the ortho acid is so employed.

Trisphosphoric acid which may be represented by the formula H5P301o may also be used as a starting material for preparation of the catalysts of this invention; These catalytic compositions may also be prepared from the siliceous materials mentioned herein and phosphoric acid mixture containing ortho-phosphoric, pyro-ph'o sphoric, tri-phosphoric, and other poly-phosphoric acids. Another acid of phosphorus which may be employed in the manufacture of composite catalysts according to the present invention is tetra-phosphoric acid. It has the general formula I-IsP4013 which corresponds to the double oxide formula 3H2O.2P2O5 which'in turn may be considered as the acid resulting when three'mole cules of water are lost by four molecules of ortho-phosphoric acid H3PO4. The tetra-phosphoric acid may be manufactured by the gradual and controlled dehydration by heating of ortho-phosphoric acid or pyro-phosphoric acid or by adding phosphorus pentoxide to these acids in'proper amounts. When the latter procedure is followed, phosphoric anhydride is added gradually until it amounts to 520% by weight of the total water present. After a considerable period of standing at ordinary temperature, the crystals of the tetra-phosphoric acid separate from the viscous liquid and it is found that these crystals melt at approximately 93 F. and have a specific gravity of 1.1886 at a temperature of 6.0 F. However, it is unnecessary to crystallize the tetra-phosphoric acid before employing it .in the preparation of the solid catalyst inasmuch as the crude tetra-phosphoric acid mixture may be incorporated with the siliceous adsorbent and other catalyst ingredient.

The materials which may be employed as adsorbents or carriers for acids of phosphorus are divided roughly into two classes. The first class comprises materials of predominantly siliceous character and includes diatomaceous earth, kieselguhr, and artificially prepared porous silica. The second class of materials which may be employed either alone or in conjunction with the first class comprisesgenerally certain members of theclass of aluminum silicatesand includes such naturally occurring substances :as various 'fullers earths and clays such as :bentonite, montmorillonite, acid treated clays and the like. Each adsorbentor supporting material which may be used will exert its own specific influence upon the net eifectiyeness of the catalyst composite which will not necessarily :be identical with that of other members of the class.

Catalysts may be prepared from an acid of phosphorus such as ortho-phosphoric acid or a polyphosphoric acid including pyrophosphoric acid, triphosphoric acid, or tetraphosphoric acid, and a siliceous adsorbentcontaining a compound selected from the members of the group consisting of an oxide, .a hydroxide, and a salt of a metal selectedfrom the members of the left hand column of group IV of the periodic table. A salt which is so used in the preparation of our composite catalysts includes particularly .a carbonate, asulfide, and a halide such as a chloride or bromide. These mentioned starting materials used in this catalyst preparation process are subjected to the steps of mixing the group IV metal compound with the siliceous adsorbent, .and thereafter mixing the phosphoric acid with the mixture of finely divided siliceous adsorbent and oxide, hydroxide or salt. The mixing with the phosphoric acidis generallycarried out at a temperature of from about to about 450 F. to form a rather wet paste, particularly :since the phosphoric acid is ordinarily the major constituent used in forming the composite. Also the group IV metal compound may be added first to the phosphoric acid or the different catalyst :ingredients may be mixed in any order to form a composite.

The resultant wet paste which is so formed from the phosphoric acid, siliceous adsorbent. and group IV metal compound is then formed into shaped particles by extrusion or other suitable means .and the resultant particles are then dried at a temperature of from about 200 to :about 500 F. to form a substantially solid material which is then calcined further at a temperature generally of from about 500 to about 1000" F. fora time gasoline.

4 of from about 0.25 to about 10 hours. The calcining may be carried out by heating in a substantially inert gas, such as air, nitrogen, and the like.

The resultant catalyst which .has been calcined is active for polymerizing olefinic hydrocarbons particularly for polymerizing normally gaseous olefinic hydrocarbons to form normally liquid hydrocarbons suitable for use as constituents of 'When employed in the conversion of olefinic hydrocarbons into polymers, the calcined catalyst formed as herein set forth is preferably employed as agranular layer in a heated reactor, which is generally made from steel, and through which :the preheated olefin-containing hydrocarbon fraction is directed. Thus the solid catalyst of this process may be employed for treating mixtures of olefin-containing hydrocarbon vapors to effect olefin polymerization, but this same catalyst may also be used at operating conditions, suitable for maintaining liquid phase operation during polymerization of olefinic hydrocarbons, such as butylenes, to produce gasoline fractions. Thus when employed in the polymerization of normally gaseous olefins, the formed and calcined catalyst particles are generally placed in a vertical, cylindrical treating tower and the olefin containing gas mixture is passed downwardly therethrough at a temperature of from about 350 to about 550 F. and at .a pressure of from about to about .1500 pounds per square inch when dealing with olefin-containing materials such as stabilizer reflux which may contain from approximately 10 to 50% or more of propylene and butylene. When operating on a mixture comprising essentially butanes and butylenes, this catalyst is effective at conditions favoring the maximum utilization of both normal butylenes and isobutylene which involves mixed polymerization at temperatures of from approximately 250 to about 325 F. and at pressures of from about 500 to about 1500 pounds per square inch.

In utilizing the catalyst of this invention for promoting miscellaneous organic reactions, the

; catalyst may be employed in essentially the same way as it is used when polymerizing olefins in case the reactions are essentially vapor phase, and it may be employed in suspension in liquid phase in various types of equipment.

With suitable modifications in the details of operation, the present type of catalyst may be employed in a large number of organic reactions, including polymerization of olefins as already mentioned. Typical cases of reaction in which the present type of catalyst may be used are the alkylation of cyclic compounds with olefins, the cyclic compounds including aromatics, polycyclic compounds, naphthenes, andphenols; condensation reactions such as those occurring between ethers and aromatics, alcohols and aromatics, phenols and .aldehydes, etc. Reactions involving the hydro-'halogenation of unsaturated organic compounds, isomerization reactions, ester formation by the interaction of carboxylic acids, and olefins, and the like. The specific procedure for utilizing the present type of catalyst in miscellaneous organic reactions will be determined by the chemical and physical characteristics and the phase of the reacting constituents.

During use of these catalysts in vapor phase polymerizations and other vapor phase treatments of organic compounds, it is often advisable to add small amounts of moisture to prevent excessive dehydration and subsequent decrease in catalyst activities. In order to substantially prevent loss of water from the catalyst. an amount of water or water vapor such as steam is added to the charged olefin-containing gas so as to substantially balance the vapor pressure of the catalyst. about 0.1 to about 6% by volume of the organic material charged.

Solid phosphoric acid catalysts which have been prepared heretofore by calcining composites of a siliceous adsorbent and a phosphoric acid frequently lose their activities during polymerization use and also sufier a marked decrease in crushing strength due to softening of the catalyst. Such softenin of the catalyst also results in short catalyst life inasmuch as the catalyst towers become plugged during use.

As an important feature of this invention, .we have found, however, that catalysts of good crushing strength may be produced by adding to the composite of phosphoric acid and diatomaceous earth, a relatively small amount of a member of the group of compounds consisting of an oxide, a hydroxide, and a salt of a metal selected from the members of the left hand column of group IV of the periodic table, which is generally added in an amount of not more than 10% and preferablyfrom about 0.5 to about 5% by weight of the catalyst mixture. A catalyst formed by drying and calcining such a composite containing a group IV metal compound also has a good crushing strength after it has been used in the polymerization of normally gaseous olefins to form normally liquid olefins. Pyrophosphoric acid-diatomaceous earth mixtures to which at least one of the above indicated compounds has been added and then the resultant composite has been dried and calcined, have been found to produce catalysts having ahigh resistance to crushing duringuse. This resistance to crushing during use is indicated by a high crushing strength both before and after use in polymerizing olefinic hydrocarbons. Such catalysts are tested for example by contacting a propanepropylene fraction therewith in a rotatable steel autoclave maintained at a temperature of about 450 F. for a time of about 2 hours. During such a test from about 30 to about 65% of the propylene charged is converted into normally liquid polymers.

The following examples of the preparation of catalysts comprised within the scope of this invention and the results obtained in their use for catalyzing the polymerization of propylene are characteristic, although the exact details set forth in these examples are not to be construed as imposing undue limitations upon the generally broad scope of the invention.

Table I shows comparative results obtained in autoclave tests on phosphoric acid-diatomaceous earth catalysts containing a member of the group consisting of an oxide, a hydroxide, anda salt of a metal selected from the mem bers of the left hand column of group IV of the periodic table. These catalyst activity tests were carried out by placing 10 grams of 5x5xmm. pellets of the catalyst and 100 grams of propane-propylene mixture (50-55% propylene content) in a rotatable steel autoclave of 850 cc. capacity rotated at a temperature of 450 F. for two hours. the end of this time, determinations were made to indicate the percentage conversion of propylene into liquid polymers.

This amount of water vapor varies from 5 TABLE I Olefin polymerization activity and crushing strength results obtained on catalysts prepared from phosphoric acid, diatomaceous earth and oxides of titanium, zirconium, and thorium [Test Conditions: 10 grams catalyst, grams propane-propylene feed (5055 mole percent CQHQ) two hours at 450 1?. (232 C.) in

850 cc. rotating autoc1ave.]

Material added to Calculation Perggi fi i Run mixture of pyrocent No phgspihogic acid Conv. an ia omace- Q o ous earth C3115 g is? 1 None Commercial 66 11. 4 5. 4 2 do 860 1 48 16.0 9. 1 3. 1.8% Titanium (11- 500 1 29 25. 8+ 19. 9

oxide. 4 do 860 1 64 21. 1+ 12. 0 5 .do 950 1 44 20. 2 21. 1 0 4.6% Zirconium di- 500 1 22 19. 4 19. 2

oxide. 7 .-do 860 1 56 21. 4 15. 7 8- 3.7% Thorium di- 500 1 4 21.0 19.0

oxide.

As indicated in the above table, a commercial. solid phosphoric acid catalyst prepared from diatomaceous earth and pyrophosphoric acid but containing no additional compound had a propylene polymerizing activity of 66% in the autoclave test but showed an after use crushing strength of only 5.4 pounds in comparison with a before use crushing strength of 11.4 pounds.- Similarly a diatomaceous earth phosphoric acid catalyst which had been given an additional calcination treatment for one hour at a temperature of 860 F'. gave a propylene conversion of 48% and retained an after use crushing strength of 9.4 pounds which was considerably lower than the initial crushing strength of 16 pounds.

The addition of 1.8% bygweight of titanium dioxide to a diatomaceous earth-pyrophosphoric acid mixture yielded a composite which after drying and calcination as indicated in Table I had a propylene polymerizing activity of between 29 and 64%, an initial crushing strength of 20 to 26 pounds and an after use crushing strength of 12 to 21 pounds. It is thus noted that the addi tion of this relatively small amount of titanium dioxide improved considerably the crushing strength of the resultant catalyst composite over that of the pyrophosphoric acid-diatomaceous earth catalyst.

Similarly, the addition of 4.6% of zirconium dioxide produced finished catalysts with propylene conversion activities of 22 to 56%, initial crushing strengths of 19-21 pounds and after use crushing strengths of 16 to 19 pounds.

The catalyst used in run 8 was produced by adding 3.7% of thorium dioxide to the pyrophosphoric acid-diatomaceous earth mixture and then calcining at a temperature of 500 F. for one hour. This catalyst had a rather low activity, 4% of propylene conversion, but had an after use crushing strength of 19 pounds in comparison with an initial crushing strength of 21 pounds.

' Further details concerningthe preparation of a the catalyst composites tested in runs 3 to Sin- The paste-like material was then heated in an evaporating dish on a water bath under a heat lamp until theconsistency of the pasty material 7. was suitable for pressingutinto a pill mold which consisted ofa steel sheet of 5 mm. thickness containlng 100 drill holes of 5 mm. internal diameter. Ihe mold plate filled with the catalyst material was then dried in an oven for 3.0 minutes at a temperature of 392 F., the pills were pressed from the plate and dried for an additional 30 minutes at the same temperature, and then dried further for 2 hours at 500 F. in a muffle furnace. The composition of the resultant catalyst mixture was calculated as 22.1% diatomaceous earth, 76.1% of orthophosphoric acid and 1.3% :of titanium dioxide.

The catalyticma'terial used inruns Band 7 was prepared from 43.9 grams .of diatomaceous earth, 9.7 grams of zirconium dioxide, and 84.3 grams of orthophosphoric acid containing 85% Illa-P04. In this preparation mentioned, the two solids were intimately mixed and the phosphoric acid was then added with further mixing. lh-e mixture was heated in an open vessel to give a paste suitable for filling into the aforementioned pill plate. The resulting pills or pellets were punched from the pill .plate :after :a preliminary drying at a-temperature of 392 F..-for.30.minutes, then were dried at the same temperature .for .30 minutes more and calcined .for .one :hour .at a temperature of 500 F. .to yield .dry .catalyst pellets with :an average bulk density of 0.84 :and :an average crushing strength of 19.4 pounds. "The scomposition calculated upon the basis of the startingmaterials was 20.8% diatomaceous earth, 74.5% of orthophosphoric acid and 4.6% of zirconium dioxide. As indicated in'Table I, the catalyst used in -7 ccrresponded'to that used in run 6 after receiving an additionalcalcination treatment for one hour at a temperature of 860 F.

The catalyst of run 8 was prepared from 43.3 grams of diatomaceous earth, 7.4 grams --of thorium dioxide and 176.1 grams of orthophosphoric acid, of 05% I-Is'PO4 concentration. Following the same procedure used in preparing the above indicated catalysts containing zirconium, the resultant catalyst in the form of 5 x5 mm. pellets was given a calcination for one hour at a temperature of 500 F. after which the catalyst pellets had an average bulk density or" 0.86 and an average crushing strength of 21 pounds. The calculated composition of this catalyst is 21.8% of diatomaceous earth, 74.5% of orthophosphoric acid, and 3.7% of thorium dioxide.

We claim as our invention:

1. A process for manufacturing ia'solid catalyst which comprises mixing at least 50% 'by'weight of a phosphoric acid, an uncalcined siliceous adsorbent, and not over approximately '10 by weight of a member of the group of compounds consisting of an oxide, a hydroxide, and a salt of a metal of the left hand column of group .IV of the periodic table, pelleting the resultant mixture, and calcining the pellets at .a temperature of from about 500 to about .1000

2. A process for manufacturing a solid catalyst which comprises mixing at least 59% by weight of a phosphoric acid, :an uncalcined siliceous adsorbent, and not over approximately 210% by weight of titanium oxide, pelleting the resultant mixture, and calcining the pellets ata temperature of from about 500 to about 1000 F. p

3. A process for manufacturing a solid catalyst which comprises mixing at "least 50% by weight of a phosphoric acid, an uncalcined siliceous adsorbent, and not over approximately -l0 by 'Weight of zirconium oxide, pelleting the re- 8 sultant mixture. and ica'lcinmg the pellets at a temperature of .from about 500 07052190111; 1000" F.

.4. .A process for z-manufacturing a solid catalyst which comprises mixing at least 5.0% by 'weight of a, phosphoric acid, an uncalcined siliceous adsorbent, and not over approximately 10% by weight of thorium oxide, pelleting the resultant mixture, and calcining the pellets at a temperatinve :of from about 500 to about 1000 F.

5. A processfor manufacturing a solid catalyst which comprises mixing at least 50% by weight of a rpolyphosphoric acid, uncalcined diatomaceous earth, and not over approximately 10% by weight of a, member of the group consisting of an oxide,:a hydroxide, and a salt of a metal of the left hand column of group IV of "the periodic table to form a composite, pelleting said composite, and calcining the pellets at a temperature of fromabout500 to about 1000 F.

Aiprocess for manufacturing asolidcatalyst which comprises mixing from about 50 to about by weight of a phosphoric acid, from about 15 to about 49.5% by weight of an uncalcined siliceous adsorbent, and from about 0.5 to about 10% .by weight of amember of the group of compounds consisting of an oxide, a hydroxide, and asalt .ofa metalof the'le'ft hand column of group IV of the periodic table to forma composite, :pellet-ing :said composite, and calcining the pellets at a temperature of from about .500 to about 1000 F.

7. .A process for manufacturing a solid catalyst which comprises mixing from about 50 to about 7.5% by weight of a phosphoric .acid, from about 15 to about 49.5% 'by weight of an uncalcined siliceous adsorbent, and Tfrom about 0.5 to about 10% by weight of titanium dioxide to form a composite, pelletingsaid composite, and calcining the pellets at a temperature of from about 500 to about 1000" F.

8. A process for manufacturing a'solid catalyst which comprises pelleting a mixture of from about 50 to about 75% by weight of a phosphoric acid, from about 15 to about 49.5% by wei ht of an uncalcined siliceous adsorbent, and from about 0.5 to about 10% by weight of zirconium dioxide, and'calcining the pellets at a temperature of from about 500 to about 1000 F.

9. A process for manufacturing a solid catalyst which comprises pelleting a mixture of from about 50 to about 75% by weight of a phosphoric acid, from about 15 to about 49.5% by weight of an uncalcined siliceous adsorbent, and from 0.5 to about 10% by weight of thorium dioxide, and calcining .the pellets at a temperature of from about 500 to about '1000 F.

MITCHELL S. BIELAW'SKI. J ULIALN M. MAVITY.

References Cited in the file of this patent UNITED S".l'.A".IES PATENTS 

1. A PROCESS FOR MANUFACTURING A SOLID CATALYST WHICH COMPRISES MIXING AT LEAST 50% BY WEIGHT OF A PHOSPHORIC ACID, UNCALCINED SILICEOUS ADSORBENT, AND NOT OVER APPROXIMATELY 10% BY WEIGHT OF A MEMBER OF THE GROUP OF COMPOUNDS CONSISTING OF AN OXIDE, A HYDROXIDE, AND A SALT OF A METAL OF THE LEFT HAND COLUMN OF GROUP IV OF THE PERIODIC TABLE, PELLETING THE RESULTANT MIXTURE, AND CALCINING THE PELLETS AT A TEMPERATURE OF FROM ABOUT 500* TO ABOUT 1000* F. 